DE2159759C3 - Nb deep 2 0 deep 5 -containing borosilicate glasses of medium to high refractive index, relatively large dispersion and high chemical resistance, as well as processes for their production - Google Patents

Nb deep 2 0 deep 5 -containing borosilicate glasses of medium to high refractive index, relatively large dispersion and high chemical resistance, as well as processes for their production

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Publication number
DE2159759C3
DE2159759C3 DE2159759A DE2159759A DE2159759C3 DE 2159759 C3 DE2159759 C3 DE 2159759C3 DE 2159759 A DE2159759 A DE 2159759A DE 2159759 A DE2159759 A DE 2159759A DE 2159759 C3 DE2159759 C3 DE 2159759C3
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Prior art keywords
deep
glasses
refractive index
percent
weight
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DE2159759B2 (en
DE2159759A1 (en
Inventor
Heinz Dipl.-Chem. 6331 Hermannstein Broemer
Norbert 6330 Wetzlar Meinert
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Ernst Leitz Wetzlar GmbH
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Ernst Leitz GmbH
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Priority to DE2159759A priority Critical patent/DE2159759C3/en
Priority to GB4505672A priority patent/GB1358650A/en
Priority to FR7237875A priority patent/FR2161929B1/fr
Priority to JP47110414A priority patent/JPS5127450B2/ja
Priority to US309804A priority patent/US3877953A/en
Publication of DE2159759A1 publication Critical patent/DE2159759A1/en
Publication of DE2159759B2 publication Critical patent/DE2159759B2/en
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Publication of DE2159759C3 publication Critical patent/DE2159759C3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S501/00—Compositions: ceramic
    • Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
    • Y10S501/903—Optical glass, e.g. silent on refractive index and/or ABBE number having refractive index less than 1.8 and ABBE number less than 70

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Description

a) 30 bis 42 Gewichtsprozent SiO2 + B2O3, davon 22 bis 30 Gewichtsprozent SiO2 und 8 bis 14 Gewichtsprozent B2O3,a) 30 to 42 percent by weight SiO 2 + B 2 O 3 , of which 22 to 30 percent by weight SiO 2 and 8 to 14 percent by weight B 2 O 3 ,

b) 9 bis 22 Gewichtsprozent K2O undb) 9 to 22 percent by weight of K 2 O and

c) entweder 37 bis 53 Gewichtsprozent Nb2O5 oder 37 bis 58 Gewichtsprozent (Nb2O5 +X), wobei im zweiten Fall der Nb2O5-GeIIaIt 2 bis 53 Gewichtsprozent beträgt und X eine der nachfolgenden Verbindungen bis zum angegebenen Höchstwert bedeutet: bis zu IG Gewichtsprozent eines Oxids der Elemente Li, Mg, Al, Bi; bis zu 20 Gewichtsprozent eines Oxids der Elemente Na, Te, bis zu 30 Gewichtsprozent eines Oxids der Elemente Ca, Sr, Ba, Zn, Cd, Pb, In, La, Sb, bis zu 35 Gewichtsprozent TiO2, bis zu 38 Gewichtsprozent Ta2O5, bis zu 10 Gewichtsprozent eines *s Fluoride der Elemente Li, Na, Ca, Al, bis zu 20 Gewichtsprozent eines Fluorids der Elemente Mg, Sr, bis zu 30 Gewichtsprozent eines Fluorids der Elemente Ba, Pb, bis zu 30 Gewichtsprozent KHF2, bis zu 30 Ge- *> wichtsprozent K2TiF6.c) either 37 to 53 percent by weight of Nb 2 O 5 or 37 to 58 percent by weight (Nb 2 O 5 + X), where in the second case the Nb 2 O 5 gel is 2 to 53 percent by weight and X is one of the following compounds up to the specified Maximum value means: up to IG percent by weight of an oxide of the elements Li, Mg, Al, Bi; up to 20 percent by weight of an oxide of the elements Na, Te, up to 30 percent by weight of an oxide of the elements Ca, Sr, Ba, Zn, Cd, Pb, In, La, Sb, up to 35 percent by weight TiO 2 , up to 38 percent by weight Ta 2 O 5, up to 10 weight percent of a * s fluorides of the elements Li, Na, Ca, Al, up to 20 weight percent of a fluoride of the elements Mg, Sr, up to 30 percent by weight of a fluoride of Ba, Pb, up to 30 weight percent KHF 2, up to 30 overall *> weight percent K 2 TiF 6th

2. Gläser nach Anspruch 1, dadurch^ gekennzeichnet, daß der Gesamtgehalt an Alkalioxiden bis 41 Gewichtsprozent beträgt2. Glasses according to claim 1, characterized ^ characterized in that the total content of alkali oxides to 41 percent by weight

3. Verfahren zur Herstellung von Gläsern nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß sie im Temperaturbereich von 1200 bis 13000C erschmolzen werden.3. Process for the production of glasses according to Claims 1 and 2, characterized in that they are melted in the temperature range from 1200 to 1300 ° C.

40 Alkalioxiden bestehen, sind nicht nur seit langem bekannt, sondern auch technisch und wissenschafthch40 alkali oxides exist aren't just for a long time known, but also technically and scientifically

Die Erfindung betrifft Nb2Os-haltige Borosilikatgläser mit verbesserten Eigenschaften und ein Verfahren zu ihrer Herstellung.The invention relates to Nb 2 O s -containing borosilicate glasses with improved properties and a method for their production.

Gläser für optische Zwecke, die aus Gemengesätzen erschmolzen werden, die aus SiO2, B2O3 undGlasses for optical purposes that are melted from batches composed of SiO 2 , B 2 O 3 and

leicht erscflmelzDar unu «cut« ^ ~— :~"easy to meltDar unu «cut« ^ ~ - : ~ "

nischen Aufwand schlieren- und blasenarme optische G1SrNachteil dieser bekannten optischen Gläser hegVim wesentlichen darin, daß sie verhältnismäßig St durch die Atmosphärilien angreifbar sind Man hat daher die Zusammensetzung der Glaser durch Zugabe von Oxiden aus der zweiten unddritten Gruppe des Periodensystems weiter auszubilden versucht, und zwar insbesondere durch Zugabe von CaO und einen mehr oder weniger großen Zusatz von AUO, Durch diese Substanzen konnte die hydrolytische Klasse der Gläser etwas verbessert dAfrican effort streaks and bubble poor optical G1 S r disadvantage of this known optical glasses hegVim essentially in that they St are relatively vulnerable to the atmospheric agencies have therefore the composition of the Glaser attempts continue to be formed by the addition of oxides from the second and third group of the Periodic Table, in particular by adding CaO and a more or less large addition of AUO. These substances could improve the hydrolytic class of the glasses somewhat d

erden·earth·

Es sind auch bereits Gläser mit ähnlicher optischer Lace bekannt (»Schwerflinte«), die im wesentlichen aus SiO2 und PbO bzw. SiO2, PbO und La2O3 bestehen. Sie haben jedoch den Nachteil daß sie bei höheren PbO-Gehalten zumeist recht fleckenempfindlich werden und daher erhebliche Schwiengkeiten bei der Großfertigung von Optiken bereitenThere are also glasses with similar optical lace known ("heavy shotgun"), which essentially consist of SiO 2 and PbO or SiO 2 , PbO and La 2 O 3 . However, they have the disadvantage that at higher PbO contents they are usually quite sensitive to stains and therefore cause considerable difficulties in the large-scale production of optics

Die Aufgabe der vorliegenden Erfindung besteht demgemäß darin, die Nachteile der bekannten optischen Gläser mit mittleren bis hohen Brechzahlen und relativ großer Dispersion zu beseitigen und solche Gläser zu schaffen, die eine hohe chemische Beständigkeit aufweisen, die farbarm sind und die sich außerdem gut zu Preßlingen verarbeiten lassen.The object of the present invention is accordingly to overcome the disadvantages of the known optical Eliminate glasses with medium to high refractive indices and relatively large dispersion and such To create glasses that have a high chemical resistance, that are low in color and that are different can also be easily processed into pellets.

Die Aufgabe wird erfindungsgemaß durch Glaser der in den Ansprüchen angegebenen, sich aus den Gemengen ergebenden Zusammensetzungen gelöst.The object is according to the invention by glazier specified in the claims, emerge from the Mixtures resulting compositions dissolved.

Ein» andere Möglichkeit der Variation im Rahmen der Erfindung besteht darin, daß der Fluorid-Zusatz auch mittels eines Alkaü-Hydrogenfluonds oder eines komplexen Alkali-Hexafluorotitanats erfolgt.Another possibility of variation within the scope of the invention is that the fluoride addition also by means of an Alkaü-Hydrogenfluonds or one complex alkali hexafluorotitanate takes place.

Diese Gläser haben die weiteren Vorteile, daß sich die entsprechenden Gemengesätze sehr leicht und bei relativ tiefen Temperaturen einschmelzen lassen, daß die Gläser schlieren- und blasenarm herstellbar sind und daß die optische Lage dieser Gläser den heutigen Wünschen und Forderungen der rechnenden Optiker weit entgegen kommt und damit eine breite Einsatzmöglichkeit in der optischen Fertigung gegeben ist.These glasses have the further advantages that the corresponding batches are very easy and with Allow relatively low temperatures to melt down so that the glasses can be produced with few streaks and bubbles and that the optical position of these glasses meets today's wishes and demands of the calculating optician comes far to the contrary and thus a wide range of possible uses in optical manufacturing is given.

Die Ausfiihrungsbeispiele der Erfindung sind in den folgenden Tabellen veranschaulicht.The exemplary embodiments of the invention are illustrated in the tables below.

Tabelletable

Kennzahlidentification number

I 4I 4

(Gewichtsprozent)(Weight percent)

30,030.0 28,528.5 28,528.5 25,925.9 23,523.5 22,422.4 11,011.0 13,513.5 10,510.5 9,59.5 8,68.6 8,28.2 22,022.0 21,021.0 21,021.0 19,019.0 17,217.2 16,416.4 37,037.0 37,037.0 40,040.0 45,645.6 50,750.7 53,053.0 1,67481.6748 1,68681.6868 1J0681J068 1,75901.7590 1,77751.7775 1,79421.7942 30,330.3 31,531.5 29,629.6 26,326.3 25,525.5 24.424.4

SiO2 SiO 2

B2O3 B 2 O 3

Nb2O5....Nb 2 O 5 ....

In Tabelle 1 sind Gläser angegeben, die ausschließ- 6s Prozent vorhanden, wobei der Anteil dieser Glaslich aus den vier Hauptbestandteilen SiO2, B2O3, bildner dann im unteren Teil des angegebenen Be-K2O und Nb2O5 bestehen. Die echten Glasbildner reiches liegt, wenn eine höhere Brechzahl gewünscht 80 BO) sind zwischen 30 und 42 Gewichts- wird. Der Tabelle kann weiterhin entnommen werden,Table 1 shows glasses that are only 6s percent present, the proportion of this glassy consisting of the four main components SiO 2 , B 2 O 3 , then forming the lower part of the stated Be-K 2 O and Nb 2 O 5 . The real glass formers are rich if a higher refractive index is desired 80 BO) are between 30 and 42 weight- will be. The table can also be seen

daß der K2O-GeDaIt bei steigender Brechzahl sinkt and daß der Nb2O5-GeIIaIt um so größer zu wählen ist je höher die Brechzahl gewünscht wird. Es konnte überraschend festgestellt werden, daß die aus diesen Gemengen erschmolzenen Gläser selbst bei hohem Nb7O -Gehalt farblos sowie schlieren- und blasen-that the K 2 O gel decreases with increasing refractive index and that the Nb 2 O 5 gel should be chosen to be larger the higher the refractive index is desired. It was surprisingly found that the glasses melted from these mixtures are colorless and streak and bubble even with a high Nb 7 O content.

Die Tabelle 2 zeigt, daß außer K2O auch zusätzlich die Alkalioxide Li2O oder Na2O verwendet werden können.Table 2 shows that, in addition to K 2 O, the alkali oxides Li 2 O or Na 2 O can also be used.

Tabelletable

I KennzahlI key figure

Ein partieller Austausch von Nb2O5 durch das inA partial exchange of Nb 2 O 5 by the in

seinen chemischen und glastechnischen Eigenschaften sehr ähnliche Ta2O5 wird in Tabelle 3 dargestellt Ta 2 O 5 , which is very similar to its chemical and glass properties, is shown in Table 3

Dabei bleiben die Gehalte der beiden GlasbildnerThe contents of the two glass formers remain

und des Alkalioxides jeweils konstantand the alkali oxide are each constant

Tabelle 3Table 3

SiO2-.SiO 2 -.

B2O3 K2O..B 2 O 3 K 2 O ..

Nb2O5 U2O .Nb 2 O 5 U 2 O.

Na2O.Na 2 O.

ne ■ ·■ · n e ■ · ■ ·

ν Iν I -8 i-8 i 28,528.5 (Gewichtsprozent)(Weight percent) 10,510.5 28,528.5 28,528.5 21,021.0 10,510.5 105105 30,030.0 21,021.0 21,021.0 10,010.0 40,040.0 20,020.0 1,66171.6617 20,020.0 35,535.5 1,70681.7068 1,60201.6020 29,629.6 40,940.9

24,724.7

9,09.0

9,0 48,29.0 48.2

9,19.1

1,7609 30,3 SiO2...1.7609 30.3 SiO 2 ...

B2O3..B 2 O 3 ..

K2O..K 2 O ..

Nb2O5 Nb 2 O 5

Ta2O5 Ta 2 O 5

ίοίο

Kennzahlidentification number

11 I 1211 I 12

(Gewichtsprozent)(Weight percent)

1313th

28,5 28,5 28,5 28,528.5 28.5 28.5 28.5

10,5 10,5 10,5 10,510.5 10.5 10.5 10.5

21,0 21,0 21,0 21,021.0 21.0 21.0 21.0

300 20,0 100 2,0300 20.0 100 2.0

10,0 20,0 30,0 38,0 1,6874 1,6733 1,6535 1,642910.0 20.0 30.0 38.0 1.6874 1.6733 1.6535 1.6429

32,4 343 37,4 39,732.4 343 37.4 39.7

Tabelle 3 zeigt, daß mit ansteigendem Ta2O5-Gehalt an Stelle des proportional abnehmenden Nb2O5-Gehalts die Brechzahl sinkt Die Tabelle 4 veranschaulicht den Einsatz drei- und vierwertiger Metalloxide und die dadurch erreichte Variation der Brechzahlen und v-Werte.Table 3 shows that with increasing Ta 2 O 5 content, instead of proportionally decreasing Nb 2 O 5 content, the refractive index falls. Table 4 illustrates the use of trivalent and tetravalent metal oxides and the resulting variation in the refractive indices and v-values.

Tabelletable

14 I14 I. 28,528.5 ,6, 6 " 1" 1 1818th Kennzahlidentification number 2020th (Gewichtsprozent)(Weight percent) 28,528.5 28,528.5 28,528.5 28,528.5 28,528.5 * I* I 2424 10,510.5 10,510.5 10,510.5 10,510.5 10,510.5 10,510.5 28,528.5 21,021.0 28,528.5 28,528.5 21,021.0 21,021.0 21,021.0 21,021.0 21,021.0 28^28 ^ 28,528.5 SiO2 SiO 2 10,510.5 20,020.0 10,510.5 10,510.5 30,030.0 20,020.0 30,030.0 20,020.0 10,010.0 13,513.5 10,510.5 B2O3 B 2 O 3 21,021.0 20,020.0 2'.,02 '., 0 21,021.0 —- —- —- —- —- 21,021.0 21,021.0 K2OK 2 O 30,030.0 —- 10,010.0 30,030.0 —- —- —- —- —- 2,02.0 5,05.0 Nb2O5 Nb 2 O 5 30,030.0 —- 30,030.0 —- 10,010.0 20,020.0 —- —- —- —- —- Sb2O3 Sb 2 O 3 —- —- —- 10,010.0 —- —- 10,010.0 20,020.0 30,030.0 —- —- Bi2O3 Bi 2 O 3 —- 1,69381.6938 —- —- 1,63591.6359 1,65901.6590 1,71311.7131 1,73021.7302 1,74431.7443 —- —- TeO2 TeO 2 —- 31,231.2 —- —- 37,737.7 35,335.3 28,528.5 26,526.5 24,624.6 35,035.0 35,035.0 TiO2 TiO 2 1,68671.6867 1,63311.6331 1,68291.6829 1,74721.7472 1,761.76 ne n e 32,3"32.3 " 33,733.7 32,732.7 124,4124.4 23,523.5 «e«E

Auch hier wurden mit Ausnahme des Schmelzbeispiels mit der Kennzahl 23 konstante Mengen der Glasbildner und des Alkalioxids beibehalten, um die Variationsmöglichkeiten der optischen Lagen in Abhängigkeit vom Zusatz der genannten Metall(III)- und Metall(lV)-Oxide besser darstellen zu können.With the exception of the melting example with the code number 23, constant quantities were also used here the glass former and the alkali oxide are retained in order to allow the possible variations of the optical positions depending on the addition of the mentioned metal (III) - and metal (IV) oxides to be better represented.

Die Beispiele mit den Kennzahlen 20 bis 24 zeigen, daß mit steigendem Gehalt an TiO2 die Brechzahl und die CH: -rsion der Gläser stark ansteigen. Diese Gläser sin·? uotz der hohen TiO2-Gehalte überraschenoV: wis-'r farbarm und relativ stabil, dadurch sind sie fu; die rechnenden Optiker sehr interessant. An Stei'o V'AO Titandioxid kann das Titan auch in Form anderer Verbindungen in das Gemenge eingesetzt werden, insbesondere in komplexer Form alsThe examples with the codes 20 to 24 show that with increasing TiO 2 content, the refractive index and the CH: erosion of the glasses rise sharply. These glasses are ·? Despite the high TiO 2 content, they are surprising: they are poor in color and relatively stable, which makes them fu; the computing opticians very interesting. On Stei'o V'AO titanium dioxide, the titanium can also be used in the mixture in the form of other compounds, in particular in complex form as

Alkali-Hexafluorotitanat, beispielsweise als K1TiF6.Alkali hexafluorotitanate, for example as K 1 TiF 6 . In Tabelle 5 sind hierfür einige Beispiele angerührt.Some examples of this are given in Table 5. Tabelletable

SiO2 . B2O3. K2O . Nb2O5 SiO 2 . B 2 O 3 . K 2 O. Nb 2 O 5

2525th

26 Kennzahl26 Key figure

(Gewichtsprozent)(Weight percent)

2828

2929

3030th

28,528.5

10,5 21,0 40,010.5 21.0 40.0

28,5 10,5 21,0 10,028.5 10.5 21.0 10.0

28,5 10,5 21,0 15,0 28,5
10,5
21,0
20,028.5 10.5 21.0 15.0 28.5
10.5
21.0
20.0

28,528.5 28,528.5 28,528.5 10,510.5 1(U1 (U 10,510.5 21,021.0 21,021.0 21,021.0 25,025.0 30,030.0 35,035.0

Fortsetzungcontinuation

33 30,0
1,5922
39,030.0
1.5922
39.0 26
(26th
( Kennzahl
27
Gewichtsprozent)identification number
27
Weight percent) 2828 2929 3030th K2TiF6....
nm K 2 TiF 6 ....
n m 1,7068
29,61.7068
29.6 25,0
1,6195
36,325.0
1.6195
36.3 20,0
1,6307
35,420.0
1.6307
35.4 15,0
1,6562
33315.0
1.6562
333 10,0
1,6708
32,210.0
1.6708
32.2 5,0
1,68045.0
1.6804 31,931.9

Hier wurde die Zusammensetzung der drei Hauptbestandteile (SiO2 + B2O3 + K2O) wieder konstant gehalten und nur die Anteile Nb2O5 und K2TiF6 systematisch verändert, wobei die Summe der Nb2os- und K2liF0-Anteile sich jeweils zu 40 Gewichtsprozent ergänzen. , .. w,Here the composition of the three main components (SiO 2 + B 2 O 3 + K 2 O) was kept constant again and only the proportions of Nb 2 O 5 and K 2 TiF 6 were systematically changed, the sum of the Nb 2 o s - and K 2 liF 0 parts each add up to 40 percent by weight. , .. w ,

Nach einer weiteren Ausbildung der Erfindung werden Fluoride aus der Reihe der Elemente Li, Na, Mg, Ca, Sr, Ba, Pb und Al sowie die Verbindungen KHF2 partiell gegen Nb2O5 ausgetauscht, wobei die drei weiteten Hauptbestandteile (SiO2, B2O3, K2O) wieder konstant gehalten werden.According to a further embodiment of the invention, fluorides from the series of the elements Li, Na, Mg, Ca, Sr, Ba, Pb and Al as well as the compounds KHF 2 are partially exchanged for Nb 2 O 5 , the three main components (SiO 2 , B 2 O 3 , K 2 O) are kept constant again.

In Tabelle 6 sind eine Reihe von solchen Beispielen angeführt.A number of such examples are given in Table 6. Tabelletable

SiO2 .SiO 2 .

LiF ..LiF ..

SrF2..SrF 2 ..

BaF2 .BaF 2 .

AlF3 .AlF 3 .

3131

3232

3333

3434

Kennzahlidentification number

35 I35 I.

(Gewichtsprozent)(Weight percent)

3737

3838

3939

4040

28,5 10,5 21,0 30,0 10,028.5 10.5 21.0 30.0 10.0

1,6657 35,71.6657 35.7

28,5 10,5 21,0 30,028.5 10.5 21.0 30.0

10,010.0

1,63861.6386

37,337.3

28,5 10,5 21,0 33,028.5 10.5 21.0 33.0

10,010.0

1,6382 36,21.6382 36.2

28,5 10,5 21,0 20,028.5 10.5 21.0 20.0

20,020.0

1,6127 41,11.6127 41.1

28,5 10,5 21,0 30,028.5 10.5 21.0 30.0

10,010.0

1,6551 36,81.6551 36.8

28,5 10,5 21,0 30,028.5 10.5 21.0 30.0

28,5
10,5
21,0
20,028.5
10.5
21.0
20.0

20,020.0

1,6268
41,91.6268
41.9

28,5
10,5
21,0
30,028.5
10.5
21.0
30.0

10,010.0

1,6642 36,41.6642 36.4

28,5 10,5 21,0 20,028.5 10.5 21.0 20.0

20,020.0

1,6380 41,21.6380 41.2

28,5 10,5 21,0 10,028.5 10.5 21.0 10.0

30,030.0

1,60661.6066

48,248.2

Tabelle 6 (Fortsetzung)Table 6 (continued)

4141

4242

4343

Kennzahl IKey figure I

(Gewichtsprozent)(Weight percent)

4545

4646

4747

SiO2 B2O3 . K2O . Nb2O5, LiF .. NaF... KHF2 MgF2 CaF2 . SrF2.. BaF2 . PbF2 . AIF3 .SiO 2 B 2 O 3 . K 2 O. Nb 2 O 5 , LiF .. NaF ... KHF 2 MgF 2 CaF 2 . SrF 2 .. BaF 2 . PbF 2 . AIF 3 .

ne n e

re r e

28,5 10,5 21,0 30,028.5 10.5 21.0 30.0

10,0 1,6234 34,510.0 1.6234 34.5

28,5 10,5 21,0 30,028.5 10.5 21.0 30.0

10,010.0

1,6422 36,11.6422 36.1

28,5 10,5 21,0 20,028.5 10.5 21.0 20.0

20,020.0

1,5874 43,31.5874 43.3

28,5 10,5 21,0 10,028.5 10.5 21.0 10.0

30,030.0

1,5410 49,91.5410 49.9

28,5
10,5
21,0
30,028.5
10.5
21.0
30.0

10,010.0

1,6760
32,91.6760
32.9

28,5 10,5 21,0 20,028.5 10.5 21.0 20.0

20,020.0

1,66171.6617

34,534.5

28,5 10,5 21,0 10,028.5 10.5 21.0 10.0

30.030.0

1,6298 37,11.6298 37.1

Es wurde festgestellt, daß schon ein sehr kleiner Gehalt an Nb2O5 im Gemenge genügt, um Gläser zu erschmelzen, die einer guten hydrolytischen Klasse angehören.It was found that even a very small amount of Nb 2 O 5 in the mixture is sufficient to melt glasses belonging to a good hydrolytic class.

Eine wertvolle Hilfe zur Einstellung von gewünschten optischen Werten — ohne Stabilität der Gläser zu verschlechtern — bietet der partielle Austausch von Nb2O5 gegen ein Oxid der Elemente: Mg, Ca, Sr, Ba, Zn, Cd und Pb, und zwar bis zu einer Höchstgrenze von 30 Gewichtsprozent. Beim überschreiten derselben konnte beobachtet werden, daß — beispielsweise im Fall des Einsatzes von Blei(ll)-Oxid — die aus den Gemengen erschmolzenen Gläser weicher werden. The partial exchange of Nb 2 O 5 for an oxide of the elements: Mg, Ca, Sr, Ba, Zn, Cd and Pb, up to a value, is a valuable aid in setting the desired optical values - without impairing the stability of the glasses a maximum of 30 percent by weight. If the limit was exceeded, it could be observed that - for example in the case of the use of lead (II) oxide - the glasses melted from the batches become softer.

Dazu einige Beispiele in der folgenden Tabelle 7:Some examples in the following table 7:

4848 4949 5050 5151 Tabelle 7Table 7 (Gev(Gev Kcnnzah
54
vichtsproCount
54
vichtspro 1
55
zcnt)1
55
zcnt) 5,5, 5757 5858 5959 6060 28,5
10,5
21,0
30,0
10,028.5
10.5
21.0
30.0
10.0 28,5
10,5
21,0
30,028.5
10.5
21.0
30.0 28,5
10,5
21,0
10,028.5
10.5
21.0
10.0 28,5
10,5
21,0
30,028.5
10.5
21.0
30.0 5252 28,5
10,5
21,0
30,028.5
10.5
21.0
30.0 28,5
10,5
21,0
10,028.5
10.5
21.0
10.0 28,5
10,5
21,0
30,028.5
10.5
21.0
30.0 28,5
10,5
21,0
10,028.5
10.5
21.0
10.0 28,5
10,5
21,0
30,028.5
10.5
21.0
30.0 28,5
10,5
21,0
10,028.5
10.5
21.0
10.0 28,5
10,5
21,0
30,028.5
10.5
21.0
30.0 28,5
10,5
21,0
10,028.5
10.5
21.0
10.0 SiO, SiO, 10,010.0 30,030.0 __ 28,5
10,5
21,0
10,028.5
10.5
21.0
10.0 _._. __ B,O, B, O, __ 10,010.0 __ __ K,O K, O __ 30,030.0 10,010.0 30,030.0 __ __ Nb,O, Nb, O, —- __ „ " _._. 10,010.0 30,030.0 χιαΠχι α Π 1,65181.6518 —- —- —- —- —- 10,010.0 30,030.0 10,0
1,687710.0
1.6877 IVIgVJ
CaO IVIgVJ
CaO 36,536.5 1,68351.6835 1,65071.6507 1,67441.6744 --- 1,67851.6785 1,62591.6259 1,67551.6755 1,62001.6200 1,67711.6771 1,63001.6300 32,132.1 30,0
1,667530.0
1.6675 SrO ....SrO .... 36,336.3 46,746.7 36,136.1 1,62091.6209 35,835.8 46,846.8 34,034.0 43,543.5 34,334.3 41,341.3 33,533.5 BaO BaO 47,347.3 ZnO ZnO CdO CdO row
η row
η ν. ν.

Aber auch 3wertige Metalloxide können erfolgreich in Gemengesätze zum Erschmelzen von erfindungsgemäßen Gläsern eingesetzt werden. Tabelle 8 zeigt einige Beispiele, in welchen Al2O3, In2O3 und La2O3 verwendet wurden.However, trivalent metal oxides can also be used successfully in batch formulations for melting glasses according to the invention. Table 8 shows some examples in which Al 2 O 3 , In 2 O 3 and La 2 O 3 were used.

Tabelle 8Table 8

6161

6262

Kennzahlidentification number 6464 6363 Gewichtsprozent)Weight percent) 28,528.5 28,528.5 10,510.5 10,510.5 21,021.0 21,021.0 30,030.0 10,010.0 30,030.0 10,010.0 —- 1,68081.6808 1,62311.6231 353353 42,142.1

SiO2 ..
B2O3--K2O ..
Nb2O5.
Al2O3 .
In2O3 .
La2O3.SiO 2 ..
B 2 O 3 --K 2 O ..
Nb 2 O 5 .
Al 2 O 3 .
In 2 O 3 .
La 2 O 3 .

28,5 10,5 21,0 30,0 10,028.5 10.5 21.0 30.0 10.0

1,6665 3431.6665 343

28,5 10,528.5 10.5

21,0 . 30,021.0. 30.0

10,010.0

1,6661 34,21.6661 34.2

284 10,5 21,0 10,0284 10.5 21.0 10.0

30,0 1,648730.0 1.6487

IKe Herstellung der erfindungsgemäßen Gläser erfolgt zweckmäßig in PlatingefäBen bei Temperature zwischen 1200 und 13000C Nach dem Einschmelzen des Gemengesatzes wird bei 14000C geläutert ui homogenisiert und dann auf Abgußtemperatur abgekühlt sowie in üblicher Weise abgegossen.IKe producing the glasses according to the invention is advantageously carried out in PlatingefäBen at Temperature 1200-1300 0 C. After the melting of the batch recipe is refined at 1400 0 C ui homogenized and then cooled to casting temperature and poured in the usual way.

Claims (1)

IO to Patentansprüche:IO to patent claims: 1. Nb2O5-haltige B jrosilikatgläser mittlerer bis hoher Brechzahl, relativ großer Dispersion und hoher chemischer Beständigkeit, gekennzeichnet durch folgende, sich aus dem Gemenge ergebende Zusammensetzung:1. B jrosilicate glasses containing Nb 2 O5 with a medium to high refractive index, relatively large dispersion and high chemical resistance, characterized by the following composition resulting from the batch:
DE2159759A 1971-12-02 1971-12-02 Nb deep 2 0 deep 5 -containing borosilicate glasses of medium to high refractive index, relatively large dispersion and high chemical resistance, as well as processes for their production Expired DE2159759C3 (en)

Priority Applications (5)

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DE2159759A DE2159759C3 (en) 1971-12-02 1971-12-02 Nb deep 2 0 deep 5 -containing borosilicate glasses of medium to high refractive index, relatively large dispersion and high chemical resistance, as well as processes for their production
GB4505672A GB1358650A (en) 1971-12-02 1972-09-29 Borosilicate glass
FR7237875A FR2161929B1 (en) 1971-12-02 1972-10-25
JP47110414A JPS5127450B2 (en) 1971-12-02 1972-11-06
US309804A US3877953A (en) 1971-12-02 1972-11-27 Niobium pentoxide-containing borosilicate glasses

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GB1506916A (en) * 1974-07-24 1978-04-12 Jenaer Glaswerk Schott & Gen Optical glass
JPS5269915A (en) * 1975-12-10 1977-06-10 Hoya Glass Works Ltd Glass for lens of eyeglasses
JPS52132012A (en) * 1976-04-30 1977-11-05 Nippon Chemical Ind Optical glass
JPS5334871U (en) * 1976-08-31 1978-03-27
DE2828791C2 (en) * 1977-07-01 1986-07-31 Corning Glass Works, Corning, N.Y. Glass in the system SiO? 2? -TiO? 2? -ZrO? 2? -CaO-BaO-Nb? 2? O? 5? -Alkalioxide (-Al? 2? O? 3? - SrO) -MgO- Refractive index and a low density
JPS54112915A (en) * 1978-02-24 1979-09-04 Nippon Chemical Ind Optical glass
GB2051773B (en) * 1979-06-12 1983-04-07 Standard Telephones Cables Ltd Fluorine containing glasses
US4400473A (en) * 1980-07-14 1983-08-23 Schott Glaswerke Acidproof, hydrolysis-resistant optical and ophathalmic glass of low density
DE3026605C2 (en) * 1980-07-14 1983-07-07 Schott Glaswerke, 6500 Mainz Acid-proof, hydrolytically stable optical and ophthalmic borosilicate glass of low density
FR2590888A1 (en) * 1985-11-29 1987-06-05 Corning Glass Works LOW-DENSITY, HIGH-REFRACTIVE LOW-DISPERSION OPHTHALMIC LENSES
US5320985A (en) * 1992-10-01 1994-06-14 Kabushiki Kaisha Ohara Low refractive optical glass of a flint glass type
JP3113604B2 (en) * 1997-03-25 2000-12-04 株式会社オハラ Optical glass with negative anomalous dispersion
US6568219B1 (en) * 2000-07-31 2003-05-27 Lucent Technologies Inc. SrO + BaO + Nb2O5 + TeO2 ceram-glass electro-optical device and method of making
US7320949B2 (en) * 2002-04-02 2008-01-22 Kabushiki Kaisha Ohara Optical glass
EP1350770A1 (en) * 2002-04-02 2003-10-08 Kabushiki Kaisha Ohara Optical glass
JP4496763B2 (en) * 2003-11-06 2010-07-07 日本電気硝子株式会社 Optical glass for mold press molding
JP5545917B2 (en) * 2008-01-31 2014-07-09 株式会社オハラ Optical glass
JP7195040B2 (en) * 2015-12-07 2022-12-23 株式会社オハラ Optical glass, preforms and optical elements
JP7294327B2 (en) * 2018-04-23 2023-06-20 株式会社ニコン Optical glass, optical element, optical system, camera interchangeable lens, and optical device using the same
US11667561B2 (en) 2018-11-26 2023-06-06 Corning Incorporated Glass material with a high index of refraction
US11591253B2 (en) 2018-11-29 2023-02-28 Corning Incorporated High refractive index silicate glass compositions with reduced devitrification kinetics

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US3460954A (en) * 1964-05-21 1969-08-12 Bendix Corp Bao-nb2o5-sio2 glass compositions for use in fiber-optics
FR1429951A (en) * 1964-05-21 1966-02-25 Glass Designers Glass compositions
US3503764A (en) * 1967-01-20 1970-03-31 Bendix Corp Core glass for fiber-optic structures having high index of refraction
US3716385A (en) * 1969-04-11 1973-02-13 Jenaer Glaswerk Schott & Gen Optical glasses comprising aif3 having a varying partial dispersion

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JPS5127450B2 (en) 1976-08-12
FR2161929B1 (en) 1976-08-20
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DE2159759B2 (en) 1974-04-11
US3877953A (en) 1975-04-15
DE2159759A1 (en) 1973-06-07
FR2161929A1 (en) 1973-07-13
JPS4865211A (en) 1973-09-08

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